Highly Efficient Copper-Catalyzed Formation of N-Aryl Diazoles Using KF/Al₂O₃

Abstract

A simple and efficient method for the coupling of aryl ­iodides with heterocyclic compounds such as diazoles that does not require the use of alkoxide bases is described. The C-N bond forming procedure shows that the combination of air stable CuI and 1,10-phenanthroline in the presence of KF/Al₂O₃ comprises an extremely efficient and general catalyst system for the N-arylation of aryl ­iodides. Different functionalized aryl iodides were coupled with ­diazoles using this method.

Key words

diazole - aryl iodides - copper iodide - coupling reaction - potassium fluoride on alumina

References and Notes

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19

Satisfactory physical and spectral data were obtained in accordance with the structure. Selected physical and spectral data are as follows.
Entry 3: colorless solid; mp 96-98 °C (Lit. [21] 98 °C). ¹H NMR (90 MHz, CDCl₃): δ = 8.1 (1 H, s), 7.8 (1 H, m), 7.6-7.3 (8 H, m). Anal. Calcd for C₁₃H₁₀N₂: C, 80.38; H, 5.20; N, 14.42. Found: C, 80.43; H, 5.14; N, 14.41.
Entry 5: brown solid; mp 60-62 °C (Lit. [9b] 60-61 °C). ¹H NMR (90 MHz, CDCl₃): δ = 7.7 (1 H, br s), 7.3-7.1 (4 H, m), 7.12 (1 H, s), 6.8 (1 H, s), 3.9 (3 H, s). Anal. Calcd for C₁₀H₁₀N₂O: C, 68.94; H, 5.78; N, 16.08. Found: C, 68.71; H, 5.67; N, 16.01. Entry 6: liquid. ¹H NMR (90 MHz, CDCl₃): δ = 7.8-7.5 (4 H, m), 7.2-6.9 (2 H, m), 6.5 (1 H, s), 3.9 (3 H, s). Anal. Calcd for C₁₀H₁₀N₂O: C, 68.94; H, 5.78; N, 16.08. Found: C, 68.81; H, 5.56; N, 16.19.
Entry 10: yellow oil. ¹H NMR (90 MHz, CDCl_3:) δ = 7.5 (1 H, s), 7.4-7.1 (5 H, m), 7.1 (1 H, s), 2.2 (3 H, s). Anal. Calcd for C₁₀H₁₀N₂: C, 75.73; H, 6.47; N, 17.70. Found: C, 75.91; H, 6.35; N, 17.80.